Reaction of the silylene Si[(NCH2But)2C6H4-1,2] with the alkali metal silylamides M[N(SiMe3)R](M = Li, Na or K; R = SiMe3 or SiMe2Ph)

The thermally stable silylene Si[(NCH(2)Bu(t))(2)C(6)H(4)-1,2] 1 undergoes oxidative addition reactions with the alkali metal silylamides MN(SiMe(3))(2)(M = Li, Na or K) to afford the new alkali metal amides MN(SiMe(3))[(1)SiMe(3)][M = Li (2), Na (3) or K (4)]. Reaction of two equivalents of 1 with LiN(R)(SiMe(3)) leads in a two-step process to the compound LiN[(1)R][(1)SiMe(3)][R = SiMe(2)Ph (5) or SiMe(3) (6)]. Alternatively, 1 reacts with 3 to afford NaN[(1)SiMe(3)](2) (7). The structures of 2-5 and are presented and the formation of 2-7 is discussed.     

(Ph)3PBr][Br7], [(Bz)(Ph)3P]2[Br8], [(n-Bu)3MeN]2[Br20], [C4MPyr]2[Br20], and [(Ph)3PCl]2[Cl2I14]: extending the horizon of polyhalides via synthesis in ionic liquids

The five polyhalides [(Ph)(3)PBr][Br(7)], [(Bz)(Ph)(3)P](2)[Br(8)], [(n-Bu)(3)MeN](2)[Br(20)], [C(4)MPyr](2)[Br(20)] ([C(4)MPyr] = N-butyl-N-methylpyrrolidinium), and [(Ph)(3)PCl](2)[Cl(2)I(14)] were prepared by the reaction of dibromine and iodine monochloride in ionic liquids. The compounds [(Ph)(3)PBr][Br(7)] and [(Bz)(Ph)(3)P](2)[Br(8)] contain discrete pyramidal [Br(7)](-) and Z-shaped [Br(8)](2-) polybromide anions. [(n-Bu)(3)MeN](2)[Br(20)] and [C(4)MPyr](2)[Br(20)] exhibit new infinite two- and three-dimensional polybromide networks and contain the highest percentage of dibromine ever observed in a compound. [(Ph)(3)PCl](2)[Cl(2)I(14)] also consists of a three-dimensional network and is the first example of an infinite polyiodine chloride. All compounds were obtained from ionic liquids as the solvent that, on the one hand, guarantees for a high stability against strongly oxidizing Br(2) and ICl and that, on the other hand, reduces the high volatility of the molecular halogens.     

Chloro- und Polyselenoselenate(II) Darstellung,Struktur und Eigenschaften von [Ph3(C2H4OH)P]2[SeCl4] · MeCN, [Ph4P]2[Se2Cl6] und [Ph4P]2[Se(Se5)2]

Chloro- and Polyselenoselenates(II): Synthesis, Structure, and Properties of [Ph₃(C₂H₄OH)P]₂[SeCl₄] · MeCN, [Ph₄P]₂[Se₂Cl₆], and [Ph₄P]₂[Se(Se₅)₂] By symproportionation of elemental selenium and SeCl₄ in polar protic solvents the novel chloroselenates(+II), [SeCl₄]^2? and [Se₂Cl₆]^2?, could be stabilized; they were crystallized with voluminous organic cations. They were characterized from complete X-ray structure analysis. Yellow-orange [Ph₃(C₂H₄OH)P]₂[SeCl₄] · MeCN (space group P1 , a = 10.535(4), b = 12.204(5), c = 16.845(6) Å, α = 77.09(3)°, β = 76.40(3)°, γ = 82.75(3)° at 140 K) contains in its crystal structure monomeric [SeCl₄]^2? anions with square-planar coordination of Se(+II). The mean Se? Cl bond length is 2.441 Å. In yellow [Ph₄P]₂[Se₂Cl₆] (space group P1 , a = 10.269(3), b = 10.836(4), c = 10.872(3) Å, α = 80.26(3)°, β = 79.84(2)°, γ = 72.21(3)° at 140 K) a dinuclear centrosymmetric [Se₂Cl₆]^2? anion, also with square-planar coordinated Se(+II), is observed. The average terminal and bridging Se? Cl bond distances are 2.273 and 2.680 Å, respectively. From redox reactions of elemental Se with boranate/thiolate in ethanol/DMF the bis(pentaselenido)selenate(+II) anion [Se(Se₅)₂]^2? was prepared as a novel type of a mixed-valent chalcogenide. In dark-red-brown [Ph₄P]₂[Se(Se₅)₂] (space group P2₁/n, a = 12.748(4), b = 14.659(5), c = 14.036(5) Å, β = 108.53(3)° at 140 K) centrosymmetric molecular [Se(Se₅)₂]^2? anions with square-planar coordination of the central Se(+II) by two bidentate pentaselenide ligands is observed (mean Se? Se bond lengths: 2.658 Å at Se(+II), 2.322 Å in [Se₅]_2?). The resulting six-membered chelate rings with chair conformation are spirocyclically linked through the central Se(+II). The vibrational spectra of the new anions are reported.     

Derivatization of deltahedral Zintl ions by nucleophilic addition: [Ph-Ge9-SbPh2]2- and [Ph2Sb-Ge9-Ge9-SbPh2]4-

The type of the reactions of addition of exo-bonded groups to deltahedral Zintl ions such as Ge9(n-) has been established as addition of anionic nucleophiles. Various nucleophiles such as Ph2Bi-, Ph2Sb-, Ph- interact with the relatively low-lying LUMO of Ge9(2-) and/or the half filled HOMO of Ge9(3-) and bond to the clusters. The title anions, characterized in their (K-crypt) salts where crypt = 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo-[8.8.8]-hexacosane, and the previously characterized [Ph2Sb-Ge9-SbPh2](2-) are made by a reaction of K4Ge9 with SbPh3 in ethylenediamine. [Ph-Ge9-SbPh2](2-) is the first ogranically functionalized deltahedral Zintl ion, i.e., a deltahedral ion with a direct carbon-cluster covalent bond, that can exists without the substituents as well. The Ge(9) clusters resemble tricapped trigonal prisms with one elongated edge (one of the three edges parallel to the pseudo 3-fold axis). The two substituents are always bonded to the vertexes of such an elongated edge. The same is true for the intercluster bond in [Ph2Sb-Ge9-Ge9-SbPh2)](4-).     

Insertion reactions of GaCp*, InCp* and In[C(SiMe3)3] into the Ru-Cl bonds of [(p-cymene)RuIICl2]2 and [Cp*RuIICl]4

The first carbonyl free ruthenium/low valent Group 13 organyl complexes are presented, obtained by insertion of ER (ER = GaCp*, InCp*, In[C(SiMe(3))(3)]) into the Ru-Cl bonds of [(p-cymene)RuCl2]2, [Cp*RuCl]4 and [Cp*RuCl2]2. The compound [(p-cymene)RuCl2]2 reacts with GaCp*, giving a variety of isolated products depending on the reaction conditions. The Ru-Ru dimers [{(p-cymene)Ru}2(GaCp*)4(mu3-Cl)2] and the intermediate [{(p-cymene)Ru}2(mu-Cl)2] were isolated, as well as monomeric complexes [(p-cymene)Ru(GaCp*)3Cl2], [(p-cymene)Ru(GaCp*)2GaCl3] and [(p-cymene)Ru(GaCp*)2Cl2(DMSO)]. The reaction of [Cp*RuCl]4 with ER gives "piano-stool" complexes of the type [Cp*Ru(ER)3Cl](ER = InCp*, In[C(SiMe3)3], GaCp*. The chloride ligand in complex can be removed by NaBPh4, yielding [Cp*Ru(GaCp*)3]+[BPh4]-. The reaction of [Cp*RuCl2]2 with GaCp* however, does not lead to an insertion product, but to the ionic Ru(II) complex [Cp*Ru(GaCp*)3]+[Cp*GaCl3]-. The ER ligands in complexes 3, 5, 6, 7 and 8 are equivalent on the NMR timescale in solution due to a chloride exchange between the three Group 13 atoms even at low temperatures. The solid state structures, however, exhibit a different structural pattern. The chloride ligands exhibit two coordination modes: either terminal or bridging. The new compounds are fully characterized including single crystal X-ray diffraction. These results point out the different reactivities of the two precursors and the nature of the neutral p-cymene and the anionic Cp* ligand when bonding to a Ru(II) centre.     

Reactivity of [(Ph2Si)2O3]4[Al(OH)]4 and [(Ph2Si)2O3]4[Al(OLi)]4 towards NaOEt and LiOH. Synthesis of New Twelve‐membered Alumopolysiloxane Rings

The reaction between [(Ph₂Si)₂O₃]₄[Al(OH)]₄ ( 1 ) or [(Ph₂Si)₂O₃]₄[Al(OLi)]₄ ( 2 ) with sodium ethoxide, or lithium hydroxide in presence of CuI·H₂O leads to the formation of new alumopolysiloxane compounds. Indeed, transformations of 1 under the partial incorporation of the reactants are found giving rise to new heteroleptic inorganic macrocycles. The molecular structure of [(Ph₂Si)₂O₃]₄[Al(ONa)]₂[Al(OH)(NaOEt)]₂·2Et₂O ( 3 ) and [(Ph₂Si)₂O₃]₄[Al(OLi)]₂[Al(OH)(LiOH)]₂·2Et₂O·2THF ( 4 ) have been determined by single‐X‐ray diffraction analysis. Both alumosiloxanes 3 and 4 are constituted by a twelve‐membered ring.     

配合物[1-(4′-bromo-2′-fluorobenzyl)pyridinium]2[Ni(mnt)2]和[1-(4′-bromo-2′-fluorobenzyl)pyrazinium]2[Ni(mnt)2](mnt2-=maleonitriledithiolate dianion)的合成及晶体结构

本文报道两个含双(马来二氰基二硫烯)镍(Ⅱ)配合物阴离子的离子对化合物。对阳离子为1-(4′-溴-2′-氟苄基)吡啶 盐时,生成配合物1。晶体数据:三斜晶系,空间P1群,a=0.7086(2)nm,b=1.0968(3)nm,c=1.1775(3)nm,α=69.914(5)°,β=89.495(5)°,γ=74.765(5)°,V=0.8259(4)nm³,Z=1。对阳离子为1-(4′-溴-2′-氟苄基)吡嗪鎓盐时,生成配合物2。晶体数据:单斜晶系,空间群P2₁/n,a=0.71554(17)nm,b=1.4262(3)nm,c=1.6725(4)nm,β=100.396(4)°,V=1.6788(7)nm³,Z=4。两个配合物中,阴离子为拟平面结构,镍原子均位于对称中心。变换对阳离子上的芳环种类对晶体的堆积结构产生影响。     

Diversity oriented synthesis: substitution at C5 in unreactive pyrimidines by Claisen rearrangement and reactivity in nucleophilic substitution at C2 and C4 in pteridines and pyrido[2,3-d]pyrimidines

Diversity oriented synthesis of fused pyrimidines leads to scaffolds with many biological activities. In the case of the preparation of pyrido[2,3-d]pyrimidines from 2-alkylthiopyrimidines, the formation of a new carbon-carbon bond at C5 is required, a reaction, that is, very limited in scope. However Claisen type rearrangement of simple 4-allylic ethers affords C5 substituted pyrimidines readily; in cases with an ester substituent, rearrangement occurs at room temperature. Subsequent cyclisation to afford 6-methylpyrido[2,3-d]pyrimidin-7(8H)-ones was achieved in high yield. Using allylic ethers derived from 3-chloromethyl-4-arylbut-3-en-2-ones as substrates, a new titanium[IV]chloride catalysed reaction affording 6-arylmethyl-7-methylpyrido[2,3-d]pyrimidines was discovered. In contrast, 2-alkylthiopteridines are readily available. In both cases, substitution at C2 and C4 to generate diversity has been carried out and the reactivity compared; yields of substitution products were generally higher with pteridine substrates. In biological assays unexpected hits were found for activity against the Gram positive bacterium, Nocardia farcinia, and against the parasite Trypanosoma brucei brucei, illustrating the value of diversity oriented synthesis in the discovery of biologically active compounds.     

Synthesis and structures of selected benzamidinates of Li, Na, Al, Zr and Sn(II) using the C1-symmetric ligands [N(SiMe3)C(C6H4Me-4 or Ph)NPh]-

Several compounds based on the C(1)-symmetric ligands [N(R)C(Ar)NPh]- [abbreviated as B1 (Ar = C(6)H(4)Me-4) or B2 (Ar = Ph), R = SiMe(3)] are reported. They are the crystalline metal benzamidinates [Li(mu:kappa2-B1)(OEt2)](2) (1), [Al(kappa2-B1)2Me] (2), [Al(kappa2-B1)2X] [X = Cl/Me, 1 : 1 (3)], [Sn(kappa2-B1)2] (4), Zr(kappa2-B1)2Cl2 (5), [Zr(kappa2-B1)3Cl] (6), [Na(mu:kappa2-B1)(tmeda)]2 (7), K[B1] (8), Li(B2)(OEt2) (9) and Zr(kappa2-B1)3Cl (10) and the known benzamidine Z-H2NC(C6H4Me-4) = NPh (11). They were prepared by (i) insertion of the nitrile 4-MeC6H4CN (1, 7, 8, 11) or PhCN (9) into the appropriate M-N(R')Ph [R' = R and M = Li (1, 9), Na (7), K (8)] bond and subsequent hydrolysis for 11 [R' = H and M = Li], or (ii) a ligand transfer reaction using the lithium amidinate 1 and Al(Me)2Cl (2, 3), SnCl2 (4) or ZrCl4 (5, 6), or Li(B2) and ZrCl4 (10). The X-ray structures of 1, 2, 3, 4, 6b (i.e..3PhMe) 7, and 11 are presented. Exploratory polymerisation experiments are described, using 2, 5 or 6 as a procatalyst with methylaluminoxane (MAO) (Al : Zr ca. 500 : 1) as promoter. Thus toluene solutions were exposed to C2H4 under ambient conditions; while 2 was unresponsive, 5 and 6 showed modest activity in the formation of polyethylene.     

Deprotonation of 1,1′-methylenebis[4-tert-butyl-2-(diphenylphosphino)-benzene] and its analogues: synthesis and crystal structure of {5-But-2-[4-But-2-(Ph2P)C6H3(Ph)CH]C6H3P(Ph)K(OEt2)}2

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Solid‐state NMR study of [(Ph3SnF)2(Ph3SnO2PPh2)], a novel coordination polymer prepared from Bu4N[Ph3SnF2] and [Ph3SnOPPh2OSnPh3](O3SCF3)

The coordination polymer [(Ph₃SnF)₂(Ph₃SnO₂PPh₂)] ( 3 ), prepared by the reaction of [Ph₃SnOPPh₂OSnPh₃](O₃SCF₃) ( 4 ) with Bu₄N[Ph₃SnF₂] ( 5 ), was investigated by multinuclear magic angle spinning magnetic resonance spectroscopy and the results compared with those of the polymeric parent compounds Ph₃SnF ( 1 ) and Ph₃SnO₂PPh₂ ( 2 ). The crystal structure of 4 was determined by X‐ray crystallography. Copyright © 2004 John Wiley & Sons, Ltd.     

Uranium (III) scorpionates: synthesis and structure of [(TpMe2)2U[N(C6H5)2]] and [(TpMe2)2U[N(SiMe3)2]

Reaction of [(Tp(Me)2)(2)UI] with KNR(2) (R = C(6)H(5), SiMe(3)) in tetrahydrofuran (THF) afforded the monomeric trivalent actinide amide complexes [(Tp(Me)2)(2)U[N(C(6)H(5))(2)]], 1, and [(Tp(Me)2)(2)U[N(SiMe(3))(2)]], 2. The complexes have been fully characterized by spectroscopic methods and their structures were confirmed by X-ray crystallographic studies. In the solid state 1 and 2 exhibit distorted pentagonal bipyramidal geometries. The U-NR(2) bond lengths in both complexes are the same but in complex 2 the greater steric demands of the N(SiMe(3))(2) ligand led to elongated U-N(pz) bonds, especially those opposite the amido ligand.     

Synthesis and structures of the [benzamidinato]3- complexes Li3(tmeda)(L1)]2 and [Li(thf)4][Li5(L2)(OEt2)2] [L1 = N(SiMe3)C(Ph)N(SiMe3) and L2 = N(SiMe3)C(C6H4-4)NPh

Reduction at ambient temperature of each of the lithium benzamidinates [Li(L(1))(tmeda)] or [{Li(L(2))(OEt(2))(2)}(2)] with four equivalents of lithium metal in diethyl ether or thf furnished the brown crystalline [Li(3)(L(1))(tmeda)] (1) or [Li(thf)(4)][Li(5)(L(2))(2)(OEt(2))(2)] (2), respectively. Their structures show that in each the [N(R(1))C(R(3))NR(2)](3-) moiety has the three negative charges largely localised on each of N, N' and R = Aryl); a consequence is that the "aromatic" 2,3- and 5,6-CC bonds of R(3) approximate to being double bonds. Multinuclear NMR spectra in C(6)D(6) and C(7)D(8) show that 1 and 2 exhibit dynamic behaviour. [The following abbreviations are used: L(1) = N(SiMe(3))C(Ph)N(SiMe(3)); L(2) = N(SiMe(3))C(C(6)H(4)Me-4)N(Ph); tmeda = (Me(2)NCH(2)-)(2); thf = tetrahydrofuran.] This reduction is further supported by a DFT analysis.     

配合物[1-(4′-fluorobenzyl)pyridinium]2[Ni(dto)2](dto2-=dithiooxalate dianion)的合成及晶体结构

The complex [1-(4′-fluorobenzyl)pyridinium]₂[Ni(dto)₂] (dto^2- means dithiooxalate dianion) has been pre-pared by reaction of Na₂[Ni(S₂C₂O₂)₂] and the 1-(4′-fluorobenzyl)pyridinium chloride salt. The crystallographic data for the title complex: triclinic P1, a=8.5698(8)?, b=9.3461(9)?, c=10.5361(10)?, α=67.177(2)°, β=67.398(2)°, γ=79.611(2)°, V=717.59(12)?³, Z=1. The [Ni(dto)₂]^2- anion with the Ni atom lying on an inversion center and exhibits a quasi-planar structure. An extensive hydrogen bond network of C-H…O is clearly observed. The nature and size of cation seems to play an important factor in the type of intermolecular interactions as well as the crystal packing in this kind of complexes.     

(C60)2Ru2Cl4[Ph2P(CH2)4PPh2]配合物的合成

在氮气氛中采用配体取代法合成了C60以σ-π配位方式与Ru形成的稳定η2型富勒烯双核钌金属配合物(C60)2Ru2Cl4[Ph2P(CH2)4PPh2],其结构经UV,IR,XPS,XRD和元素分析表征.